Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/02—Halogenated hydrocarbons
  • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S260/00—Chemistry of carbon compounds
  • Y10S260/24—Flameproof

Definitions

• This invention relates to flame retardant glass reinforced thermoplastic polyester compositions. More particularly, it pertains to self-extinguishing and non-buming compositions comprising a normally flammable linear high molecular weight polyester, filamentous glass reinforcement, a flame retardant additive and an amount of polytetrafluoroethylene sufficient to retard dripping.
• polyesters have not been widely accepted for use as molding resins, however, until only fairly recently, because of their relative brittleness in thick sections when crystallized from the melt. This problem was overcome by varying the crystal texture, e.g., by using two step molding cycles or including nucleating agents, and by molecular weight control. This permitted the marketing of injection moldable poly(ethylene terephthalates) which typically. in comparison with other thermoplastics, offer a high degree of surface hardness and abrasion resistance, and lower surface friction.
• thermoplastic polyesters particularly when reinforced with glass fibers, are very useful materials, their application has been severly hindered by the fact that they burn readily and are extremely difficult to render fire retardant.
• polyesters have a tendency to drip while burning, and it is difficult to prevent the dripping even with fibrous glass reinforcement,- and c. polyesters are subject to serious degradation in the presence of a number of conventionally used flame retardants, with a loss in physical properties.
• thermoplastic compositions for mold ing e.g., injection molding, compression molding, transfer molding, and the like, comprising a. a normally flammable high molecular weight linear polyester resin;
• filamentous glass in an amount of from about 5 to about percent by weight based on the combined weight of the glass and the resin
• a flame-retardant additive in a minor proportion based on the composition but in an amount at least sufficient to render the polyester resin non-burning or self-extinguishing;
• a polytetrafluoroethylene resin in a minor proportion based on the composition but in an amount at least suffcient to render the polyester resin non-dripping (if burning).
• a molded piece of about 2 X V; X A inch is formed from the composition and if it does not drip upon ignition sufficiently to ignite a piece of cotton l2 inches beneath and will extinguish itself within 30 seconds, after two lO-second ignitions, the composition is deemed to be nondripping and flame-retardant to the point where it satisfies the requirements set forth by the Underwriters Laboratories.
• ASTM Test D-635 for flammability comprises contacting the end ofa specimen 1% by 5 inches and thickness normally supplied with a Bunsen burner flame for 30 seconds; and repeating if there is no ignition. If the specimen does ignite but does not continue burning to the 4 inch mark, after the flame is removed, it is classed as self-extinguishing by this test.
• the higher molecular weight, normally flammable, linear polyesters used in the present compositions are polymeric glycol esters of terephthalic acid and isophthalic acids. They are available commercially or can be prepared by known techniques, such as by the alcoholysis of esters of the phthalic acid with a glycol and subsequent polymerization, by heating glycols with the free acids or with halide derivatives thereof, and similar processes. These are described in US. Pat. No. 2,465.3 l9 and U.S. Pat. No. 3,0475 39, and elswhere.
• glycol portion of the polyester can contain from two to ten carbon atoms, it is preferred that it contain from two to four carbon atoms, in the form of linear methylene chains.
• Preferred polyesters will be of the family consisting of high molecular weight, polymeric glycol terephthalates or isophthalates having repeating units of the general formula wherein n is a whole number of from 2 to 4 and mixtures of such esters, including copolyesters of terephthalic and isophthalic acids over the entire composition range.
• polyesters are poly(ethylene terephthalate) and poly(l,4-butylene terephthalate). Special mention is made of the latter because it crystallizes at such a good rate that it may be used for injection molding without the need for nucleating agents or long cycles, as is sometimes necessary with poly(ethylene terephthalate),
• high molecular weight polyesters will have an intrinsic viscosity of at least about 0.4 deciliters/gram as measured in o-chlorophenol, a 60/40 phenol-tetrachloroethane mixture of a similar solvent at 25-30 C.
• the filamentous glass to be employed as reinforcement in the present compositions is well known to those skilled in the art and is widely available from a number of manufacturers.
• fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass.
• E lime-aluminum borosilicate glass
• C soda glass
• the filaments are made by standard processes, e.g., by steam or air blowing, flame blow ing and mechanical pulling.
• the preferred filaments for plastics reinforcement are made by mechanical pulling,
• the filament diameters range from about 0.00012 to 0.00075 inch, but this is not critical to the present invention.
• the length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings, or woven into mats, and the like, are also not critical to the invention.
• the filamentous glass in the form of chopped strands of from about one-eighth to about 2 inches long.
• articles molded from the compositions on the other hand, even shorter lengths will be encountered because, during compounding, considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by theromplastic injection molded articles in which the filament lengths lie between about 0.000005 and 0. l 25 (one-eighth) inch.
• the sized filamentous glass reinforcement comprises from about 5 to about 90% by weight based on the combined weight of glass and resin, and preferably from about 5 to about 60 percent by weight. Especially preferably the glass will comprise from about 5 to about 40 percent by weight based on the combined weight of glass and resin.
• up to about 60 percent of glass can be present without causing flow problems.
• the flame-retardant additives useful in this invention comprise a family of chemical compounds well known to those skilled in the art. Generally speaking, the more important of these compounds contain chemical elements employed for their ability to impart flame resistance, e.g., bromine, chlorine, antimony. phosphorus and nitrogen. It is preferred that the flame-retardant additive comprise a halogenated organic compound (brominated or chlorinated); a halogen-containing organic compound in admixture with antimony oxide; elemental phosphorus or a phosphorus compound; a halogencontaining compound in admixture with a phosphorus compound or compounds containing phosphorus-nitrogen bonds or a mixture oftwo or more of the foregoing.
• a halogenated organic compound brominated or chlorinated
• a halogen-containing organic compound in admixture with antimony oxide elemental phosphorus or a phosphorus compound
• the amount of flame-retardant additive used is not critical to the invention, so long as it is present in a minor proportion based on said composition major proportions will detract from physical properties but at least sufficient to render the polyester resin non-burning or self-extinguishing.
• the amount of additive will be from 0.5 to 50 parts by weight per hundred parts of resin.
• a preferred range will be from about 3 to 25 parts and an especially preferred range will be from about 8 to 12 parts ofadditive per I00 parts of resin. Smaller amounts of compounds highly concentrated in the elements responsible for flame-retardance will be sufficient, e.g..
• elemental red phosphorus will be preferred at 0.5 to 2.0 parts by weight per hundred parts of resin, while phosphorus in the form of triphenyl phosphate will be used at 25 parts of phosphate per I00 parts of resin, and so forth.
• Halogenated aromatics will be used at 8 to l2 parts and synergists, e.g., antimony oxide,will be used at about 2 to 5 parts by weight per parts of resin.
• R is an alkylene, alkylidene or cycloaliphatic linkage, e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, and the like; a linkage selected from the group consisting of ether; carbonyl; amine; a sulfur containing linkage, e.g., sulfide, sulfoxide, sulfone; a phosphorus-containing linkage; and the like.
• R is an alkylene, alkylidene or cycloaliphatic linkage, e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, and the like; a linkage selected from the group consist
• R can also consist of two or more alkylene or alkylidene linkages connected by such groups as aromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, a phosphorus-containing linkage, and the like. Other groups which are represented by R will occur to those skilled in the art.
• Ar and Ar are monoor polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and the like.
• Ar and Ar may be the same or different Y is a substituent selected from the group consisting of organic, inorganic or organometallic radicals.
• the substituents represented by Y include l halogen, e.g., chlorine, bromine, iodine, or fluorine or (2) ether groups of the general formula OE, wherein E is a monovalent hydrocarbon radical similar to X or (3) monovalent hydrocarbon groups of the type represented by R or (4) other substituents, e.g., nitro, cyano, etc., said substituents being essentially inert provided there be at least one and preferably two halogen atoms per aryl, cg, phenyl, nucleus.
• l halogen e.g., chlorine, bromine, iodine, or fluorine
• E is a monovalent hydrocarbon radical similar to X or (3) monovalent hydrocarbon groups of the type represented by R or (4) other substituents, e.g., nitro, cyano, etc., said substituents being essentially inert provided there be at least one and preferably two halogen atoms per aryl
• X is a monovalent hydrocarbon group exemplified by the following: alkyl, such as methyl, ethyl, propyl, isopropyl, bu tyl, decyl, and the like; aryl groups, such as phenyl, naphthyl, biphenyl, xylyl, tolyl, and the like; aralkyl groups, such as benzyl, ethylphenyl, and the like; cycloaliphatic groups, such as cyclopentyl, cyclohexyl, and the like; as well as monovalent hydrocarbon groups containing inert substituents therein. it will be understood that where more than one X is used they may be alike or different.
• the letter d represents a whole number ranging from l to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings comprising Ar or Ar.
• the letter e represents a whole number ranging from 0 to a maximum controlled by the number of replaceable hydrogens on R.
• the letters a, b, and c represent whole numbers including 0. When b is not 0, neither a nor 6 may be 0. Otherwise either a or c, but not both, may be 0. Where b is 0, the aromatic groups are joined by a direct carbon-carbon bond.
• hydroxyl and Y substituents on the aromatic groups, Ar and Ar can be varied in the ortho, meta or para positions on the aromatic rings and the groups can be in any possible geometric relationship with respect to one another.
• substituted benzenes exemplified by l,3-dichlorobenzene, L4- dibromobenzene, l ,3-dichloro-4-hydroxybenzene, hexachlorobenzene, hexabromobenzene, and biphenyls such as 2,2'-dichlorobiphenyl, 2,4'-dibromobiphenyl, and 2,4- dichlorobiphenyl.
• the preferred halogen compounds for this invention are aromatic halogen compounds such as chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, brominated terphenyl, or a compound comprising two phenyl radicals separated by a divalent alkylene or oxygen group and having at least two chlorine or bromine atoms per phenyl nucleus, and mixtures of at least two of the foregoing.
• aromatic halogen compounds such as chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, brominated terphenyl, or a compound comprising two phenyl radicals separated by a divalent alkylene or oxygen group and having at least two chlorine or bromine atoms per phenyl nucleus, and mixtures of at least two of the foregoing.
• hexabromobenzene and chlorinated biphenyls are especially preferred, alone, or mixed with antimony oxide.
• the preferred phosphate compounds are selected from elemental phosphorus or organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphene oxides, phosphenes, phosphites or phosphates.
• lllustrative are triphenyl phosphene oxide. This can be used alone or mixed with hexabromobenzene or a chlorinated biphenyl and,optionally, antimony oxide.
• Typical or the preferred phosphorus compounds to be employed in this invention would be those having the general formula where each represents the same or different radicals including hydrocarbon radicals such as alkyl, cycloalkyl, aryl, alkyl substituted aryl and aryl substituted alkyl; halogen; hydrogen and combinations thereof provided that at least one ofsaid Rs is aryl.
• Suitable phosphates include, phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl-bis(3,5,5-trimethylhexyl phosphate), ethyldiphenyl phosphate, 2 ethylhexyl di(ptolyl) phosphate, diphenyl hydrogen phosphate.
• bis(Z-ethylhexyl) p-tolylphosphate tritolyl phosphate, bis(Z-ethylhexyl)phenyl phosphate, tri-(nonyl-phenyl)phosphate, phenylmethyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyldephenyl phosphate, p'tolyl bis( 2,5,5 '-trimethylhexyl )phosphate, 2 ethylhexyldiphenyl phosphate, diphenyl hydrogen phosphate, and the like.
• the preferred phosphates are those where each R is aryl.
• the most preferred phosphate is triphenyl phosphate. It is also preferred to use triphenyl phosphate in combination with hexabromobenzene and, optionally, antimony oxide.
• flame-retardant additives for this invention are compounds containing phosphorus-nitrogen bonds, such as phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris(aziridinyl)phosphine oxide or tetrakis(hydroxymethyl)phosphonium chloride. These flameretardant additives are commercially available.
• the polytetrafluoroethylene resins are commercially available or can be prepared by known processes. They are white solids obtained by polymerization of tetrafluoroethylene in aqueous media with free radical catalysts, e.g., sodium, potassium or ammonium peroxydisulfates at 100 to l,000 psi. at 0200 C. and preferably at 20l00 C. See Brubaker, US. Pat. No. 2,393,967. While not essential, it is preferred to use the resins in the form of relatively large particles, e.g., of average size 0.3 to 0.7 mm, mostly 0.5 mm. These are better than the usual polytetrafluoroethylene powders, which have particles of 0.05 to 0.5 millip.
• Such preferred polytetrafluoroethylenes are designated by ASTM as Type 3, and are available commercially from the DuPont Company (TEFLON Type 6) for general use in the extrusion of thinwalled tubular goods and tape.
• compositions of this invention can be prepared by a number of procedures.
• glass roving a bundle of strands of filaments
• the fibers are shortened and predispersed in the process, coming out at less than one-sixteenth inch long.
• glass filaments are ground or milled to short lengths, and are mixed with the polyester resin, flame retardant additive and polytetrafluoroethylene resin by dry blending then either fluxed on a mill and ground, or they are extruded and chopped.
• continuous lengths of glass roving are drawn through a bath of melted polyester resin, flame retardant additive and polytetrafluoroethylene resin which coats the filaments and the resin-coated glass strand is chopped into small cylinders, one-fourth inch or longer, to form a molding compound.
• the glass fibers can also be mixed with resin and additives and directly molded. e.g., by injection or transfer molding techniques.
• compounding should be carried out to insure that the residence time in the machine is short; the temperature is carefully controlled; the frictional heat is utilized; and an intimate blend between the resin and the additives is obtained.
• Precompounding can be carried out in conventional equipment. For example, afier carefully pre-drying the polyester resin and other additives and the glass, e.g., under vacuum at C. for 12 hours, a single screw extruder is fed with a dry blend of the ingredients, the screw employed having a long transition section to insure proper melting. 0n the other hand, a twin screw extrusion machine, e.g., a 28 mm Werner Pfleiderer machine can be fed with resin and additives at the feed port and glass down stream. In either case, a generally suitable machine temperature will be about 450 to 460 F.
• the precompounded composition can be extruded and cut up into molding compounds, such as conventional granules, pellets, etc., by standard techniques.
• compositions can be molded in any equipment conventionally used for glass-filled thermoplastic compositions.
• poly( 1,4-butylene terephthalate) good results will be obtained in an injection molding machine, e.g., of the Newbury type, with conventional cylinder temperatures, e.g., 450 F. and conventional mold temperatues, e.g., l50 F.
• poly(ethylene terephthalate) because of the lack of uniformity of crystallization from interior to exterior of thick pieces, somewhat less conventional, but still well known, techniques can be used.
• a nucleating agent such as graphite or a metal oxide, e.g., ZnO or MgO, can be included and standard mold temperatures of l50-200 F. will be used; or, without such agents, mold temperatures of at least 230F. will be used.
• the dry blend is precompounded at 450 F. by passing it Flammability and physical test results are as follows: through a V4 inch Wayne single screw extruder. The screw has a long transition section to insure proper melting.
• extru- UL 94 fl mm bili (sec. lstjseclndl 5n, 4 3 2 date is pelletized and the pellets are injection molded at 450 (no dripping) F. into test bars measuring vi; X X 2% inches in a 3 02.
• the flammability tests are carried out following Un- Hem distortion lempemlufe o 1 derwriter's Laboratories Subject 94 procedures.
• a minimum 08409 of three bars are tested for burning time after two ignitions. 40 I b h d h After each lO-second) ignition. the test bar must extinguish b f 6 f a at composne g; mg to i f itself within 30 seconds. and the bar must not drip during the 0 tamed w f f flammaPll'ly 'i' burning, to be classed as non-burning or self-extinguishing.
• the composite according to this invention lngred'ems Pans by weight meets the Underwriters Laboratories Subject 94 flame retard requjremems.
• the procedure of Example 1 is ref i mi ?g peated omitting the flame retardant agent and the po y e m 0e y we polytetrafluoroethylene resin.
• the formulation is as follows:
• Example 2 For comparison purposes, the procedure of Example 1 is repeated omitting the flame retardant agent and the polytetrafluoroethylene resin. The fonnulation is as follows:
• the pellets of resin and dispersed glass are mixed with the mineral oil until they have an oily, slightly tacky, uniform coating.
• the solid fire retardants and polytetrafluoroethylene resin are added gradually and the mix is agitated manually for about minutes, then extruded in a inch Wayne Laboratory extruder at 590 F. and 50 rpm.
• the extrudate is cut into pellets and these are injection molded in a 6 oz.
• VanDom machine under the following conditions: temp., cylinder, nozzle, 450 F.; cylinder, front and middle, 470 F.; cylinder, rear, 450 F.; temperature, mold, 260 F.; Pressure injection, 200 psi; pressure, plasticizing, 100 psi; cycle time, 55 seconds.
• the dimensions of the specimens are A X A X 2% inches. Flammability and physical property test results are as follows:
• composition according to this invention containing the normally flammable poly(ethylene terephthalate) meets the Underwriter's Laboratories requirements.
• Example 4 For comparison purposes, the procedure of Example 4 is repeated omitting the flame retardant agent and the polytetrafluoroethylene resin.
• the formulation is as follows:
• this composite fails to meet the flammability requirements and, even though the flame retardant additives are absent, the physical properties, particularly flexural modulus, impact resistance and heat distortion temperature are not significantly better than those of the composition of Example 4 according to this invention.
• compositions according to this invention provide flame retardant glass fiber-reinforced molded articles.
• Example 22 The procedure of Example I is repeated substituting for the lightly sized 497 3 glass fiber reinforcement an unsized, short fiber reinforcement (Vitro-Strand, Johns-Manville Sales Corp.) The resulting composition has an exceptionally high degree of flame retardance.
• Example I The procedure of Example I is repeated, substituting for the lightly sized 497X3 glass fiber reinforcement, one containing a fire retardant sizing, prepared as follows: glass fibers containing about 1.2percent by weight of a thermoplastic styreneethyl acrylate copolymer sizing material (HR-3250, manufactured by Pittsburgh Plate Glass Co.) are dispersed in a 15 per cent by weight chloroform solution of chlorinated biphenyl (Arochlor 1,268) then the solvent is evaporated during 4 to 5 hours in a forced air oven until the glass is dry and free flow ing. The resulting composition has an exceptionally high degree of flame retardance.
• a fire retardant sizing prepared as follows: glass fibers containing about 1.2percent by weight of a thermoplastic styreneethyl acrylate copolymer sizing material (HR-3250, manufactured by Pittsburgh Plate Glass Co.) are dispersed in a 15 per cent by weight chloroform solution of chlorinated biphenyl
• poly( l,3-propylene terephthalate) prepared from trimethylene glycol and methyl terephthalate by the procedure of U.S. Pat. No. 2,465,3 l9, Example 12.
• the molding powder formulations may be used alone or mixed with other polymers and may contain various fillers, such as wood flour, diatomaceous earth, carbon black, and the like, as well as pigments and dyes, stabilizers, plasticizers, and the like.
• a flame retardant, glass reinforced thermoplastic composition for molding comprising a. a normally flammable high molecular weight linear polyester resin,
• filamentous glass in an amount of from about 5 to about percent by weight based on the combined weight of said glass and said resin
• a flame-retardant additive in a minor proportion based on said composition but in an amount at least sulficient to render said polyester resin non-burning or self-extinguishing and d. a polytetrafluoroethylene resin in a minor proportion based on said composition but in an amount at least suflicient to render said polyester resin non-dripping 2.
• said polyester is selected from the group consisting of polymeric glycol terphthalate and isophthalate esters having repeating units of the general formula nitrogen bonds; or a mixture of the foregoing, and said compound is present in an amount of from 0.5 to 50 parts by weight per hundred parts of said resin.
• said halogen containing compound is an aromatic halogen containing compound selected from the group consisting of chlorinated benzene; brominated benzene; chlorinated biphenyl; chlorinated terphenyl; brominated biphenyl; brominated terphenyl; a compound comprising two phenyl radicals separated by a divalent alkylene or oxygen group and having at least two substituents selected from the group consisting of chlorine and bromine per phenyl radical; and a mixture of at least two of the foregoing.
• composition as defined in claim 6 wherein said organic halogen compound is hexabromobenzene.
• composition as defined in claim 6 wherein said organic halogen compound is a chlorinated biphenyl.
• a composition as defined in claim 5 wherein said flame retardant additive is selected from the group consisting of elemental phosphorus; organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphine oxides, phosphines, phosphites, phosphates and mixtures of any of the foregoing.
• a composition as defined in claim 5 wherein said flame retardant additive is a mixture of hexabromobenzene, antimony oxide and triphenyl phosphate.
• a composition as defined in claim 5 wherein said flame retardant additive is a mixture of hexabromobenzene, antimony oxide and triphenyl phosphine oxide.
• a composition as defined in claim 5 wherein said flame retardant additive is a mixture of a chlorinated biphenyl and triphenyl phosphine oxide.
• thermoplastic composition for molding comprising a. a normally flammable high molecular weight linear poly( 1,4-butylene terephthalate b. filamentous glass reinforcement. in the form of dispersed fibrous chopped strands, in an amount of from 5 to 40 percent by weight based on the combined weight of said glass and said resin;
• a flame retardant additive a mixture of hexabromobenzene, from about 8 to about 12 parts by weight per hundred parts by weight of said resin, and antimony oxide, from about 2 to about 5 parts by weight per hundred parts by weight of said resin;
• a polytetrafluoroethylene resin from about 0.5 to 2.5 parts by weight per hundred parts by weight of said resin.
• composition as defined in claim 17 wherein the polytetrafluoroethylene resin has an average particle size of from about 0.3 to about 0.7 millimeters, before blending. 0.125

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• Compositions Of Macromolecular Compounds (AREA)

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Cited By (238)

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• 1971
  • 1971-05-05 US US140596A patent/US3671487A/en not_active Expired - Lifetime
• 1972
  • 1972-05-01 GB GB2006272A patent/GB1360121A/en not_active Expired
  • 1972-05-04 DE DE2221772A patent/DE2221772C2/de not_active Expired
  • 1972-05-04 JP JP4452672A patent/JPS5530024B1/ja active Pending
  • 1972-05-05 IT IT23969/72A patent/IT955231B/it active
  • 1972-05-05 NL NLAANVRAGE7206168,A patent/NL172456C/xx not_active IP Right Cessation
  • 1972-05-05 FR FR7216264A patent/FR2135354B1/fr not_active Expired

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